Carbon nanotube assembly, carbon nanotube dispersion, conductive material, electrode, secondary battery, planar assembly, filter, electromagnetic wave shield, and extreme-ultraviolet pellicle

Abstract

To provide a carbon nanotube assembly which exhibits excellent conductivity in the form of a carbon nanotube dispersion; a carbon nanotube dispersion; a conductive material; an electrode; a secondary battery, a planar assembly; a filter; an electromagnetic wave shield; and an extreme-ultraviolet pellicle.SOLUTION: A carbon nanotube assembly, a carbon nanotube dispersion, a conductive material, an electrode, a secondary battery, a planar assembly, a filter, an electromagnetic wave shield, and an extreme-ultraviolet pellicle which satisfy the conditions (1) and (2). (1) The pore volume is 0.60 cm3 / g to 5.00 cm3 / g. (2) The ratio between the volume resistivity under 20 kN pressurization and the volume resistivity under 1 kN pressurization is 0.18 to 0.30.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a carbon nanotube aggregate, a carbon nanotube dispersion, a conductive material, an electrode, a secondary battery, a planar aggregate, a filter, an electromagnetic wave shield, and a pellicle for extreme ultraviolet rays. [Background technology]

[0002] Carbon nanotubes are substances with a cylindrical structure formed by rolling up graphene sheets in which carbon atoms are arranged in a hexagonal honeycomb pattern. Carbon nanotubes are basically broadly classified into single-walled carbon nanotubes formed from a single layer of graphene sheets and multi-walled carbon nanotubes formed from multiple layers of graphene sheets. Carbon nanotubes have good mechanical and electronic properties and are expected to be used in a variety of applications. In recent years, various attempts have been proposed to further improve the properties of carbon nanotubes.

[0003] For example, Patent Document 1 describes a pore volume of 0.94 cm 3 / g or more and entangled carbon nanotubes, a method for producing the same, and a positive electrode for a primary battery are described. Patent Document 2 describes carbon nanotubes, a carbon nanotube dispersion, a carbon nanotube resin composition, and a nonaqueous electrolyte secondary battery, in which, when Z (nm) is the pore diameter of the peak top in the pore diameter distribution of carbon nanotubes with diameters of 2 nm or more and 200 nm or less calculated by the BJH method, 3≦Z≦80 is satisfied, and the pore volume in this pore diameter distribution satisfies predetermined condition (A) or (B). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-527611 [Patent Document 2] Japanese Patent Publication No. 2023-98706 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one embodiment of the present disclosure is to provide an aggregate of carbon nanotubes that has excellent electrical conductivity when made into a carbon nanotube dispersion liquid. Another problem to be solved by another embodiment of the present disclosure is to provide a carbon nanotube dispersion liquid that contains the above-mentioned aggregate of carbon nanotubes and has excellent conductivity. Another problem to be solved by another embodiment of the present disclosure is to provide a conductive material, an electrode, and a secondary battery that include the carbon nanotube aggregate. Another problem to be solved by another embodiment of the present disclosure is to provide a planar aggregate including the above carbon nanotube aggregate. Another problem to be solved by another embodiment of the present disclosure is to provide a filter, an electromagnetic wave shield, and a pellicle for extreme ultraviolet radiation using the above-mentioned planar assembly. [Means for solving the problem]

[0006] <1> An aggregate of carbon nanotubes that satisfies the following conditions (1) and (2): (1) Pore volume is 0.60 cm 3 / g~5.00cm 3 / g. (2) The ratio of the volume resistivity under a pressure of 20 kN to the volume resistivity under a pressure of 1 kN is 0.18 or more and 0.30 or less. <2> including bundle structures, <1> The carbon nanotube aggregate according to claim 1. <3> BET specific surface area is 100m 2 / g~420m 2 / g, <1> or <2> The carbon nanotube aggregate according to claim 1. <4> <1> ~ <3> 1. A carbon nanotube dispersion liquid comprising the aggregate of carbon nanotubes according to any one of 1 to 8 above and a dispersion medium. <5> <1> ~ <3> A conductive material comprising the aggregate of carbon nanotubes according to any one of the above. <6> an electrode active material; <5> and the conductive material according to claim 1. <7> <6> A secondary battery comprising the electrode according to claim 1. <8> <1> ~ <3> 1. A planar aggregate of carbon nanotubes comprising the aggregate of carbon nanotubes according to any one of 1 to 3, wherein the aggregate of carbon nanotubes has a maximum length of 1000 μm to 30000 μm. <9> <8> A filter using the planar assembly described in 1. <10> <8> An electromagnetic wave shield using the planar assembly described in 1. <11> <8> A pellicle for extreme ultraviolet radiation using the planar assembly described in . [Effects of the Invention]

[0007] According to an embodiment of the present disclosure, it is possible to provide an aggregate of carbon nanotubes that has excellent electrical conductivity when made into a carbon nanotube dispersion liquid. According to another embodiment of the present disclosure, it is possible to provide a carbon nanotube dispersion liquid containing the aggregate of carbon nanotubes and having excellent conductivity. According to another embodiment of the present disclosure, it is possible to provide a conductive material, an electrode, and a secondary battery, each including the above-described carbon nanotube aggregate. According to another embodiment of the present disclosure, a planar aggregate including the carbon nanotube aggregate can be provided. According to another embodiment of the present disclosure, a filter, an electromagnetic wave shield, and a pellicle for extreme ultraviolet rays can be provided using the above-mentioned planar assembly. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a scanning electron microscope photograph showing one embodiment of a specific CNT aggregate. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, the carbon nanotube aggregate, carbon nanotube dispersion, conductive material, electrode, secondary battery, planar aggregate, filter, electromagnetic wave shield, and pellicle for extreme ultraviolet radiation according to the present disclosure will be described in detail. The following description may be based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments and can be implemented with appropriate modifications within the scope of the object of the present disclosure.

[0010] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, when there are multiple substances corresponding to each component, the amount of each component means the total amount of the multiple substances unless otherwise specified. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0011] In the present disclosure, the terms "carbon nanotubes," "single-walled carbon nanotubes," "multi-walled carbon nanotubes," "multi-walled carbon nanotubes having a maximum length of 1000 μm to 30000 μm," "carbon nanotube aggregate," and "carbon nanotube dispersion" may be abbreviated as "CNT," "SWCNT," "MWCNT," "ULMWCNT," "CNT aggregate," and "CNT dispersion," respectively.

[0012] [Carbon nanotube aggregates] One embodiment of the present disclosure is an aggregate of carbon nanotubes that satisfies the following conditions (1) and (2). (1) Pore volume is 0.60 cm 3 / g~5.00cm 3 / g. (2) The ratio of the volume resistivity under a pressure of 20 kN to the volume resistivity under a pressure of 1 kN is 0.18 or more and 0.30 or less. Hereinafter, the carbon nanotube aggregate of this embodiment will also be referred to as a "specific CNT aggregate."

[0013] The specific CNT aggregate has excellent electrical conductivity when prepared as a carbon nanotube dispersion. That is, a carbon nanotube dispersion containing a specific CNT aggregate and a dispersion medium that satisfies the above conditions (1) and (2) (hereinafter also referred to as a "specific CNT dispersion") has excellent electrical conductivity.

[0014] The specific CNT dispersion is another embodiment of the present disclosure, and details regarding the specific CNT dispersion other than the specific CNT aggregate will be described later.

[0015] On the other hand, neither Patent Document 1 nor Patent Document 2 focuses on setting the pore volume of the CNT aggregate and the ratio of the volume resistivity under a pressure of 20 kN to the volume resistivity under a pressure of 1 kN as predetermined conditions from the viewpoint of obtaining a carbon nanotube dispersion liquid with excellent conductivity.

[0016] The specific CNT aggregate will be described in detail below. However, the speculations described in the following description are not intended to limit the interpretation of the specific CNT aggregate, but are described as an example.

[0017] <Condition (1)> The specific CNT aggregate has a pore volume of 0.60 cm 3 / g~5.00cm 3 / g, 0.60 cm 3 / g~3.20cm 3 / g is preferred.

[0018] The specific CNT aggregate has a pore volume of 0.60 cm 3 / g~5.00cm 3 / g, friction between the specific CNT aggregates falls within a suitable range, and when the specific CNT aggregates are dispersed, it is presumed that this makes it easier to stably form conductive paths, improving the conductivity of the dispersion.

[0019] In contrast, the pore volume is 0.60 cm 3 It is presumed that CNT aggregates with a density of less than 1 / g have less surface roughness, resulting in less friction between the CNT aggregates and making it difficult to maintain stable contact, resulting in an unstable conductive path.

[0020] Also, the pore volume is 5.00 cm 3 It is presumed that CNT aggregates larger than this value will be insufficiently dispersed in the dispersion liquid due to increased friction between the CNT aggregates, which is detrimental to the formation of conductive paths.

[0021] Furthermore, the pore volume is 5.00 cm 3 If the pore volume is greater than 1 / g, the number of voids in the CNT aggregate increases, which may reduce the physical strength of the CNT aggregate. This is undesirable because a reduction in the physical strength of the CNT aggregate may mean that the CNT aggregate cannot withstand a process in which shear force is applied, such as a process of dispersing the CNT aggregate (for example, the pores may be partially blocked or the CNT aggregate may be partially destroyed). Furthermore, if the pore volume is too large, the number of voids in the CNT aggregate may increase, which may result in the conductive paths in the CNT aggregate becoming too long and increasing resistance, which is undesirable.

[0022] In the present disclosure, the pore volume of a CNT aggregate is the volume (cm) of pores that a CNT aggregate has per unit mass (g). 3 The form of the CNT aggregate to be measured for pore volume is not limited, and may be in any form such as powder, fiber, or sheet.

[0023] In the present disclosure, the pore volume of the CNT aggregate is measured using a constant volume method, and a specific surface area / pore size distribution measuring device can be used as the measuring device.

[0024] Pore ​​volume of CNT aggregates (cm 3 / g) is specifically measured by the following procedure. First, a CNT aggregate to be measured is subjected to vacuum degassing treatment at 300°C for 3 hours to prepare a sample for measurement. The nitrogen adsorption and desorption isotherms of the prepared measurement samples are measured using the constant volume method. The BJH method is used for analysis to calculate the pore volume. Measurement equipment: Specific surface area / pore distribution measurement equipment (product name "BEL SORP-miniII", manufactured by Microtrack BEL) Measurement temperature: 77K Adsorbate: Nitrogen Saturated vapor pressure: Actual measurement Adsorbate cross section: 0.162nm 2 Waiting time after reaching adsorption equilibrium: 500 seconds

[0025] <Condition (2)> The specific CNT aggregate has a ratio of the volume resistivity under a pressure of 20 kN to the volume resistivity under a pressure of 1 kN (hereinafter also simply referred to as "resistivity ratio") of 0.18 or more and 0.30 or less.

[0026] Because the specific CNT aggregate has a resistivity ratio of 0.18 or higher, it does not tend to aggregate very much when in powder form and has good dispersibility in the dispersion medium, allowing it to be widely and finely dispersed in the dispersion. Therefore, it is presumed that the conductive paths formed between the CNTs in the dispersion tend to be of an appropriate length, resulting in a dispersion with excellent conductivity. Furthermore, because the specific CNT aggregate has a resistivity ratio of 0.30 or lower, the contact between the CNTs is moderately strong, making it easy for conductive paths to be stably formed, resulting in a dispersion with excellent conductivity.

[0027] In one embodiment, the resistivity ratio of the specific CNT aggregate is preferably 0.21 or more and 0.24 or less. When the resistivity ratio is 0.21 or more and 0.24 or less, the specific CNT aggregate does not have a very high tendency to aggregate in a powder state and dispersibility in a dispersion medium is easily ensured, which is presumably why communication between the CNTs finely dispersed in the dispersion can be ensured and the conductivity of the dispersion is improved.

[0028] In another embodiment, the resistivity ratio of the specific CNT aggregate is preferably 0.25 or more and 0.29 or less. When the resistivity ratio is 0.25 or more and 0.29 or less, it is presumed that the aggregation tendency in the powder state is not too high, and the conductivity of the specific CNT dispersion liquid can be more stably ensured.

[0029] In the present disclosure, the volume resistivity of the CNT aggregate is measured using a resistivity meter by a four-probe method at 25° C. A Loresta device can be used as the resistivity meter. Specifically, using a Loresta device (product name: powder resistivity measurement system MCP-PD51, low resistivity meter Loresta-GP, low resistivity probe for powder MCP-PD511 (constant current application type 4-probe method), all manufactured by Nitto Seiko Analytech Co., Ltd.), the measurement sample is introduced into the resistivity measurement probe unit, and a pressure of 1 kN or 20 kN is applied using the attached hydraulic pump. After the target load is reached, the volume resistivity (Ω·cm) is measured.

[0030] A powder of CNT aggregates is used as a sample for measuring volume resistivity. When the CNT aggregate is in a form other than powder (for example, fiber or sheet), the CNT aggregate may be pulverized to obtain a powder. The pulverization method is not particularly limited, and any pulverization method capable of crushing the CNT aggregate into small pieces may be used. As the pulverization method, a freeze-pulverization method may be used.

[0031] In the present disclosure, the resistivity ratio is calculated by dividing the measured volume resistivity under a pressure of 20 kN by the measured volume resistivity under a pressure of 1 kN, and rounding off to two decimal places.

[0032] The resistivity ratio of the CNT aggregate can be adjusted by a conventional method. Methods for adjusting the resistivity ratio of a CNT aggregate include, for example, controlling the content of impurities contained in the CNTs, controlling structural defects in the CNTs, controlling the content ratio of SWCNTs and MWCNTs, controlling the length of the CNTs, and controlling the specific surface area of ​​the CNTs.

[0033] Regarding impurities contained in CNTs, it is thought that when the load pressure is low, the impurities are trapped between the CNTs, significantly blocking the conductive path and resulting in high resistivity. On the other hand, as the load pressure increases, the number of contact points between CNTs increases, reducing the effect of the impurities on the increase in resistance and resulting in a lower resistivity. Therefore, the resistance ratio can be controlled by controlling the content of Fe atoms and / or Co atoms derived from the catalyst, which are major impurities.

[0034] The amount of structural defects in CNTs can be measured by the G / D intensity ratio in Raman spectra. When the G / D intensity ratio is high, there are fewer structural defects, which tends to result in lower resistivity. The G / D intensity ratio can be controlled by selecting the conditions for the CNT manufacturing method described below. The resistivity ratio can be controlled by adjusting the mixing ratio of CNTs with high G / D intensity ratios and CNTs with low G / D intensity ratios as needed.

[0035] In general, SWCNTs have lower resistivity than MWCNTs, and the lower the resistivity, the smaller the change in resistivity due to applied load. The number of CNT walls can be controlled by selecting the conditions for the CNT manufacturing method described below.

[0036] The longer the CNT, the lower the resistivity tends to be. Taking this into consideration, one method of control is to incorporate ULMWCNT. ULMWCNT can be obtained, for example, by controlling the manufacturing method of CNT.

[0037] The resistivity ratio of a specific CNT aggregate can also be controlled by the specific surface area of ​​the CNT. A small specific surface area makes it difficult to secure contact points between CNTs, but it is presumed that the effect of increasing contact points due to load and pressure is significant. On the other hand, a large specific surface area makes it easier to secure contact points between CNTs, but it is presumed that the effect of increasing contact points due to load and pressure is small. The specific surface area of ​​the CNT can be controlled by adjusting the conditions in the CNT manufacturing method described below. If necessary, the mixing ratio of CNTs with large specific surface areas and CNTs with small specific surface areas can be controlled and the two can be mixed uniformly.

[0038] <Bundle structure> The specific CNT aggregate preferably includes a bundle structure from the viewpoint of improving handleability. A bundle structure refers to an aggregate in which multiple CNTs aggregate together due to van der Waals forces or the like, forming a bundle. It is believed that the inclusion of bundle structures of an appropriate size in a specific CNT aggregate improves the handleability of the CNT aggregate and further improves its stability. However, if the bundle structures contained in the specific CNT aggregate become too large, the size of the CNT aggregate itself becomes too large, and it becomes difficult to separate and disperse the CNTs contained in the bundle structures, which may reduce dispersibility in a dispersion medium.

[0039] For this reason, from the viewpoint of achieving both ease of handling of the CNT aggregate and dispersibility in a solvent, the width of each bundle structure contained in the specific CNT aggregate, i.e., the size in the width direction of the fiber bundle, is preferably 5 nm to 500 nm, and more preferably 10 nm to 300 nm.

[0040] The presence or absence of a bundle structure in a specific CNT aggregate can be confirmed by observing the specific CNT aggregate with an optical microscope, a scanning electron microscope (SEM), etc. The width of the bundle structure can be determined by identifying the location where the bundle structure exists in the specific CNT aggregate and measuring the length using a photographed image of the bundle structure.

[0041] The bundle structure can be formed, for example, in the production by chemical vapor deposition (CVD method), by controlling the catalyst particle size distribution and controlling the cooling rate in the cooling process.

[0042] <BET specific surface area> The specific CNT aggregate preferably has a BET specific surface area of 100 m 2 / g to 420 m 2 / g.

[0043] When the specific surface area is small, it becomes difficult to secure contacts between CNTs, but it is presumed that the effect of increasing contacts by load pressurization is greatly manifested. On the other hand, when the specific surface area is large, it becomes easy to secure contacts between CNTs, but it is presumed that the effect of increasing contacts by load pressurization is small. It is presumed that when the BET specific surface area of the specific CNT aggregate is 100 m 2 / g to 420 m 2 / g, contacts between CNTs are secured, and the effect of increasing contacts by load pressurization is also presumed to be good.

[0044] In the present disclosure, the BET specific surface area of the CNT aggregate is determined by a gas adsorption method using nitrogen gas in accordance with JIS Z 8830:2013. As the specific surface area measuring device, for example, BELSORP-mini II (trade name), a specific surface area measuring device manufactured by MicrotracBEL Corporation, can be preferably used. However, the specific surface area measuring device is not limited to this.

[0045] The BET specific surface area of the specific CNT aggregate can be controlled by synthesis conditions such as the firing temperature, gas flow rate, and gas introduction method when synthesizing CNTs. The BET specific surface area of the specific CNT aggregate can be increased, for example, by increasing the firing temperature when synthesizing CNTs, and can be decreased by decreasing the firing temperature when synthesizing CNTs.

[0046] The specific CNT aggregate is composed of CNTs with a large specific surface area (e.g., 420 m 2 / g~1400m 2 / g) and CNTs with a small specific surface area (e.g., 10 m 2 / g~100m 2 / g) in combination.

[0047] <Other matters regarding specific CNT aggregates> In the present disclosure, the CNTs contained in the specific CNT aggregate may be SWCNTs or MWCNTs, but it is preferable that the specific CNT aggregate contains MWCNTs, as these have a wall number distribution and are slightly less uniform, making it easier to improve dispersibility.

[0048] Generally, SWCNTs have a lower volume resistivity than MWCNTs, and the lower the volume resistivity, the smaller the change in resistivity due to applied load. Therefore, in a specific CNT aggregate, SWCNTs and MWCNTs may be mixed as needed. The number of CNT walls can be controlled by selecting the CNT manufacturing method.

[0049] The longer the CNT, the lower its volume resistivity tends to be. The length of the CNT can be controlled by selecting the CNT manufacturing method.

[0050] In one embodiment, the specific CNT aggregate may be an aggregate containing MWCNTs having a maximum length of 500 μm or less as a main component, and not containing MWCNTs having a maximum length of 500 μm to 30,000 μm. Here, "main component" means that 90 mass % or more of the CNTs constituting the specific CNT aggregate are MWCNTs having a maximum length of 500 μm or less. The specific CNT aggregate may also contain SWCNTs having a maximum length of 500 μm or less.

[0051] In one embodiment, the specific CNT aggregate preferably includes MWCNTs having a maximum length of 10 μm to 30,000 μm. In one aspect, the MWCNTs preferably include ULMWCNTs.

[0052] ULMWCNT is MWCNT with a maximum length of 1000 μm to 30000 μm, which is longer than general-purpose MWCNT and can take the form of a fiber.

[0053] By taking on a fibrous form, ULMWCNTs have the property of easily entangling with each other. The MWCN contains at least one ULMWCNT, and from the viewpoint that the MWCNTs are more likely to entangle with each other and form a more stable aggregate, it is preferable that the MWCN is an aggregate containing multiple ULMWCNTs. Hereinafter, an aggregate containing ULMWCNT may be abbreviated as "ULMWCNT aggregate."

[0054] Here, the term "fiber" is generally used to refer to a structure in which one dimension is larger than the other two. The fiber may be a thread-like fiber with a circular cross section, a ribbon-like fiber with a rectangular cross section, hollow, or have another shape. From the viewpoint of increasing electrical conductivity, the cross section of the ULMWCNT is preferably circular, and hollow is preferred.

[0055] The aggregate of MWCNTs may be an aggregate having a three-dimensional structure in which the MWCNTs are entangled with one another. Figure 1 is a scanning electron microscope (SEM) photograph showing one embodiment of an aggregate of MWCNTs according to the present disclosure. The SEM photograph shown in Figure 1 reveals that multiple fibrous ULMWCNTs are entangled to form an aggregate. In this way, the entangled state of the ULMWCNTs according to the present disclosure can be confirmed by SEM observation.

[0056] The length of ULMWCNTs can be measured by focusing on a single ULMWCNT and observing multiple SEM images taken at adjacent viewing angles. Here, "ULMWCNT length" refers to the measured length of the ULMWCNT in the longitudinal direction, and the maximum value of the measured lengths is taken as the "maximum length." When observing an SEM photograph, if one MWCNT with a maximum length in the range of 1000 μm to 30000 μm is observed within the viewing angle of the SEM photograph, it can be confirmed that the observed MWCNT includes ULWMCNT.

[0057] It is preferable that multiple ULMWCNTs are present within the viewing angle of the SEM photograph. Focusing on 100 MWCNTs within the viewing angle of the SEM photograph, the maximum length of each is measured, and from the viewpoint of further improving the stability of the MWCNT aggregate due to the entanglement of ULMWCNTs, it is preferable that 10% or more of the observed MWCNTs have a maximum length in the range of 1000 μm to 30,000 μm (i.e., ULMWCNTs), calculated as numbers, be present, more preferably 20% or more, even more preferably 30% or more, and particularly preferably 50% or more.

[0058] The diameter of ULMWCNT can be measured by observing SEM or transmission electron microscope (TEM) photographs. Here, the diameter refers to the length in the direction perpendicular to the longitudinal direction of the ULMWCNT. The diameter is measured at 10 different points on one ULMWCNT, and the average value is used as the diameter of that ULMWCNT.

[0059] The length of the ULMWCNT is in the range of 1,000 μm to 30,000 μm, preferably in the range of 1,050 μm to 25,000 μm, more preferably in the range of 1,100 μm to 20,000 μm, even more preferably in the range of 1,200 μm to 18,000 μm, and particularly preferably in the range of 1,300 μm to 15,000 μm. The diameter of the ULMWCNT is preferably 1 nm to 100 nm, more preferably in the range of 2 nm to 80 nm, even more preferably in the range of 3 nm to 50 nm, and particularly preferably in the range of 5 nm to 30 nm.

[0060] The length / diameter ratio of the ULMWCNT, the so-called aspect ratio, is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 10,000 or more. The aspect ratio can be calculated from the ratio of the maximum length to the diameter of a single ULMWCNT. From the viewpoint of measurement accuracy, it is preferable to use the average value of the measurements of 20 or more ULMWCNTs.

[0061] Furthermore, from the viewpoint of dispersibility, the specific gravity of the ULMWCNT aggregate is preferably in the range of 1.5 to 2.5, more preferably in the range of 1.7 to 2.4, and even more preferably in the range of 1.8 to 2.2. The specific gravity of the ULMWCNT aggregate can be measured by the method described in JIS Z8807:2012 "Method for measuring density and specific gravity of solids."

[0062] The purity of the ULMWCNT aggregate as MWCNT can be measured by thermogravimetric analysis. For example, a thermal analyzer (Shimadzu Corporation, DTG-60) is used to obtain a thermogravimetric (TG) curve and a differential thermal analysis (DTA) curve of the ULMWCNT aggregate. The largest exothermic peak in the DTA curve, which appears at a peak top near 650°C to 750°C, is considered to be the combustion of MWCNT, and any other exothermic peaks are considered to be the combustion of substances other than MWCNT. The purity of the MWCNT is determined from the weight loss rate of the TG curve. From the viewpoint of the resulting conductivity, the purity of the ULMWCNT aggregate is preferably 50% by mass or more, more preferably 65% ​​by mass or more, even more preferably 80% by mass or more, and particularly preferably 95% by mass or more.

[0063] ULMWCNT may contain 0.01% to 50% by mass of Fe atoms derived from the iron catalyst used during production. ULMWCNT may contain Fe atoms, for example, in a state where they are adsorbed on the surface of the ULMWCNT or in a state where they are incorporated into the fibrous ULMWCNT formed during production.

[0064] The resulting fibrous ULMWCNTs are preferably flexible and strong. In addition, the conductivity of ULMWCNT itself is 5000 ohms. -1 m -1 It is preferable that it is 10,000 ohms or more. -1 m -1 It is more preferable that the conductivity of the ULMWCNT itself is 1,000,000 ohms or more. -1 m -1The following is the case.

[0065] <Method for manufacturing CNT> The method for manufacturing CNT in the present disclosure is not particularly limited. For example, as the method for manufacturing MWCNT in the present disclosure, methods such as a conventionally known chemical vapor deposition (CVD) method, a method of reacting a gaseous reactant containing a carbon source in the presence of a catalyst, etc. can be applied.

[0066] The CNT in the present disclosure can be manufactured, for example, by referring to the methods described in JP-A-2016-102047, JP-T-2021-527611, etc.

[0067] Hereinafter, the method for manufacturing CNT in the present disclosure will be described with examples. However, the method for manufacturing CNT in the present disclosure is not limited to the following examples.

[0068] =Manufacturing method X= As an example of the method for manufacturing CNT referred to in the present disclosure, the manufacturing method described in JP-A-2016-102047 can be mentioned. That is, a step of passing a gaseous reactant containing one or more carbon sources through a reactor, a step of reacting one or more gaseous reactants in the reaction region of the reactor in the presence of a catalyst to form product particles containing carbon, a step of aggregating the product particles into aggregates, and a step of applying a force to the aggregates to continuously move the aggregates outside the reaction region (hereinafter, also referred to as "manufacturing method X").

[0069] According to manufacturing method X, MWCNT containing ULMWCNT can be obtained in the form of fibrous aggregates or other aggregate forms that are easy to handle.

[0070] In manufacturing method X, the force applied to the product particles may be a mechanical force. When the agglomerates are fibrous MWCNTs, the mechanical force applied to the product particles can be exerted by a rotating spindle around which the agglomerates are wound. The fibrous MWCNTs can be collected on the spindle or can be accumulated elsewhere by rotating around the spindle one or more times and then successively unwinding the spindle.

[0071] The spindle is preferably oriented with its axis perpendicular or parallel to the flow direction of the gaseous reactant(s), although other orientations are also possible, for example, a spindle with its axis oriented at a 25° angle to the flow direction of the gaseous reactants may also be suitable for applying mechanical forces to the product particles.

[0072] The spindle can rotate around two axes (e.g., two perpendicular axes). In particular, the spindle can rotate around axes perpendicular and parallel to the flow direction of the gaseous reactants. Such a spindle can pull and twist the fibrous CNT aggregates to control the twist number and length.

[0073] The spindle may be made of metal, ceramic, or resin. The spindle can have different suitable shapes depending on the material properties and the intended use of the MWCNTs. The spindle can be used as a mold for producing carbon products, for example, by a spin-coating process. Preferred spindle shapes are rod-shaped or box-shaped.

[0074] The fibrous MWCNTs are deposited on a spindle or elsewhere, and the coating thickness and orientation can be controlled by controlling the reaction time and conditions, or by the conditions under which an electric or other field is applied to the carbon product. The coating thickness and orientation of the carbon product can be controlled, for example, by gas flow forces.

[0075] The rotation speed of the spindle is preferably 0.01 rpm (revolutions / minute; the same applies hereinafter) to 10,000 rpm, and more preferably 0.1 rpm to 100 rpm. The spinning speed (i.e., the rotational speed of the spindle) may be adjusted so that the material is collected at a similar rate as it is produced. The rotational speed of the spindle may also control the thickness of the accumulated MWCNT fiber. In a preferred embodiment, as the spindle rotates, the MWCNT fiber is processed in the axial direction of the spindle. This processing ensures that the MWCNT fiber is evenly wrapped along the spindle, rather than being wrapped only at one specific point on the spindle.

[0076] The MWCNT fibers may be collected, for example, on the reactor wall by a substrate placed in the reactor. The substrate may be a fixed substrate or a rotating guide that is used to apply a strong and equal force to the MWCNT fibers as they are collected. Suitable substrate configurations for fiber technology include a substrate consisting of two guides positioned at right angles to each other.

[0077] In production method X, the mechanical force applied to the product particles may be a force applied by an accelerating gas flow. The accelerating gas flow may be generated by passing the product particles through a reactor having a narrow diameter or through a capillary tube downstream of the reaction zone. A vacuum may be applied to the product particles.

[0078] Other forces that can be applied to the product particles include electrostatic forces, which are appropriately applied by a charged plate. Electrostatic forces require that the product particles be charged. The use of a charged plate allows the MWCNTs to grow in the form of intertwined sheets on the charged plate.

[0079] Other forces applied to the product particles may also be magnetic forces or photon pressure applied by a light source.

[0080] Instead of a gaseous reactant containing a carbon source, the CNT precursor may be injected in the form of a liquid containing a carbon source. When a liquid is used as the CNT precursor, it can be injected through a single inlet or multiple inlets, for example, in a showerhead configuration.

[0081] Preferably, the gaseous reactant(s) are reacted at a temperature between 500° C. and 1600° C., more preferably between 1000° C. and 1500° C. A temperature gradient is preferably maintained within the reactor, with the reaction zone being maintained at a higher temperature than the product zone of the reactor.

[0082] The gaseous reactants may be mixed with one or more gases that act as diluents. The gaseous reactants may also be mixed with gases that play a supporting but not direct role in the reaction. It is also preferred to use a diluent gas that can react with the amorphous carbon by-product, if any, to keep the reactive sites on the catalyst intact and produce nanotubes.

[0083] Examples of gases that can be used as diluents include argon or other inert gases, hydrogen, nitrogen, ammonia, carbon dioxide, and helium. Among these, hydrogen is particularly preferred as a gas that can be used as a diluent. The flow rate of the gas used as a diluent is preferably 2000 mL (milliliters) / min or less, and more preferably 400 mL / min to 800 mL / min.

[0084] The gas pressure of the gaseous reactants and any diluents is preferably 0.1 bar to 50 bar, more preferably 0.5 bar to 5 bar, and even more preferably 1 bar to 2 bar. If there is a gas effluent from the furnace, the effluent gas can be recycled with or without cleaning.

[0085] The composition of the product particles can be controlled by monitoring the agglomerates and modifying the reaction conditions based on the information obtained. For example, the agglomerates can be monitored by online Raman spectroscopy, which provides data indicating whether the CNTs are single-walled or multi-walled. It also provides data indicating the diameter and crystallinity of the CNTs. The agglomerates can also be monitored by online conductivity measurements, gas analysis, measuring the opacity of the reaction zone, and / or measuring the winding force.

[0086] When the agglomerate is removed from the reactor, it is preferable to prevent air from entering the reactor. When the diluent gas contains hydrogen, preventing air from entering the reactor is particularly important, for example, from the viewpoint of preventing an explosive mixture of hydrogen and air from forming in the reactor.

[0087] The product particles in production method X contain ULMWCNTs. Depending on the production conditions, SWCNTs may also be contained in addition to MWCNTs.

[0088] The product particles may be produced by chemical vapor deposition, where a gaseous reactant, a carbon source, is reacted in the presence of a catalyst.

[0089] Carbon-containing compounds suitable as carbon sources include carbon monoxide, carbon dioxide, aromatic hydrocarbons (e.g., benzene, toluene, xylene, cumene, ethylbenzene, naphthalene, or mesitylene), non-aromatic hydrocarbons (e.g., methane, ethane, propane, butane, pentane, hexane, cyclohexane, ethylene, propylene, or acetylene), and oxygen-containing hydrocarbons (e.g., formaldehyde, acetaldehyde, acetone, methanol, ethanol, diethyl ether, polyethylene glycol, 1-propanol, ethyl formate, and hydrocarbons containing mixtures of two or more thereof). The carbon-containing compound is preferably carbon monoxide, methane, ethylene or acetylene.

[0090] Preferably, the carbon source contains oxygen. Ethanol is a particularly preferred carbon source. Oxygen can be introduced into the reactor by other methods, such as by using a diluent gas or a carbon source containing water.

[0091] The gaseous reactant, which is a carbon source, is preferably injected into the reactor at a rate of 0.01 mL / min to 10 mL / min, more preferably 0.08 mL / min to 0.25 mL / min.

[0092] The catalyst is preferably a transition metal, particularly a group VIB transition metal such as chromium (Cr), molybdenum (Mo), or tungsten (W), or a group VIIIB transition metal. Specifically, the catalyst is preferably, for example, iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), or manganese (Mn), or a mixture thereof. Metals from the lanthanide and actinide series (e.g., yttrium (Y)) can also be used as catalysts. Fe, Ni, Co, Mo, and mixtures thereof, such as a mixture of Ni and Co (50 / 50 by mass), a mixture of Fe and Ni, or a mixture of Fe and Mo, are more preferred. Any of these transition metals, either alone or in combination with any of the other transition metals listed, can serve as a catalyst for CNT growth, with it being particularly preferred that the catalyst be a mixture of two or more of the listed metals.

[0093] The catalyst is preferably formed by decomposition of a precursor. The precursor is preferably a thermally, photo-, or plasma-decomposable compound of one or more of the above metals, such as a carbonyl or cyclopentadienyl organometallic compound. Ferrocene, iron pentacarbonyl, nickelocene, and cobaltocene are particularly preferred precursors. Suitably, at least 0.01% by weight of the precursor is contained in the carbon source, and preferably 0.2% to 2.5% by weight of the precursor is contained in the carbon source. In one embodiment, 0.23% to 2.3% by weight of the precursor is contained in the carbon source. The catalyst may be used supported on a carrier, and preferred carriers include silica and magnesium oxide.

[0094] The carbon source is preferably reacted in the presence of a promoter. Suitable promoters are one or more of sulfur, phosphorus, molybdenum, and organic compounds of these elements. Thiophene is also a preferred promoter. Suitably, up to 10% by weight of the promoter is included in the carbon source. Preferably, 0.2% to 6% by weight of the promoter is included in the carbon source. When high or low concentrations of thiophene are used as the promoter, MWCNTs are formed. For example, MWCNTs are successfully formed using ethanol containing 0 mass % or 1.5 mass % to 4.0 mass % thiophene and 0.5 mass % to 5.0 mass % (particularly 2.3 mass %) ferrocene under conditions of an injection rate of 3.0 mL / hour to 12.0 mL / hour (particularly 7.5 mL / hour), a hydrogen flow rate of 400 mL / min to 800 mL / min, and a synthesis temperature of 1100°C to 1180°C.

[0095] According to production method X, it is possible to obtain fibrous CNTs having a length of at least 500 μm, for example, at least 1 mm. The fibrous CNTs can be in the form of threads or sheets. The length of the fibrous CNT can be controlled, for example, by the winding capacity of the spindle used in producing the fibrous CNT.

[0096] The manufacturing method X preferably includes the steps of reacting a carbon source in a reaction zone of a reactor to produce CNTs, and aggregating the CNTs into aggregates by applying force to the CNTs. This manufacturing method makes it possible to easily produce fibrous CNTs.

[0097] In another embodiment, steps may be taken that include forming MWCNTs containing ULMWCNTs in a reaction zone by the methods described above, followed by condensing to form MWCNTs containing ULMWCNTs, and continuously withdrawing the MWCNTs from near the reaction zone. In another embodiment, the method may include producing MWCNTs containing ULMWCNTs in a reaction zone, continuously electrostatically attracting the MWCNTs containing ULMWCNTs from the reaction zone, and recovering the MWCNTs containing ULMWCNTs.

[0098] =Manufacturing method Y= In the present disclosure, the manufacturing method described in JP-A 2021-527611 can be referred to as an example of a method for manufacturing CNTs. That is, the manufacturing method includes a step (1) of supporting a mixture containing a main catalyst precursor and a co-catalyst precursor on γ-Al2O3 to manufacture an active support, a step (2) of drying the active support by multistage drying including vacuum drying, a step (3) of subjecting the dried active support to a heat treatment to manufacture a supported catalyst, and a step (4) of manufacturing CNTs in the presence of the supported catalyst (hereinafter also referred to as "manufacturing method Y").

[0099] ·Process (1) In step (1), a mixture containing a main catalyst precursor and a co-catalyst precursor is supported on γ-Al 2 O 3 to produce an active support.

[0100] In order to uniformly support the main catalyst precursor and the co-catalyst precursor on γ-AlO, the mixture may further contain a solvent, and the main catalyst precursor and the co-catalyst precursor may be dissolved in the solvent. The solvent may be one or more selected from the group consisting of water, methanol, and ethanol, and water is preferred.

[0101] Because γ-Al2O3 has high porosity and a spinel structure, the main catalyst and promoter can be randomly arranged in γ-Al2O3. CNTs grown from the randomly arranged main catalyst can be produced in an entangled state.

[0102] The main catalyst may be one or more selected from the group consisting of cobalt, iron, nickel, manganese and chromium, with cobalt being preferred.

[0103] The main catalyst precursor may be one or more selected from the group consisting of nitrates, sulfates, carbonates and acetates of the main catalyst, with nitrates of the main catalyst being preferred.

[0104] The main catalyst precursor may be one or more selected from the group consisting of Co(NO3)2, Co(NO3)2·6H2O, Co2(CO)8, Co2(CO)6[HC=C(C(CH3)3)], Co(CH3CO2)2, Fe(NO3)3, Fe(NO3)2·nH2O, Fe(CH3CO2)2, Ni(NO3)2, Ni(NO3)2·6H2O, Mn(NO3)2, Mn(NO3)2·6H2O, Mn(CH3CO2)2·n(H2O) and Mn(CO)5Br, of which Co(NO3)2·6H2O, Fe(NO3)2·nH2O and Ni(NO3)2·6H2O are preferred.

[0105] The promoter improves the dispersibility of the main catalyst, and may be one or more selected from the group consisting of vanadium and molybdenum.

[0106] The promoter precursors were NH4VO3, NaVO3, V2O5, V(C5H7O2)3, and (NH4)6Mo7O. 24 4H2O, NH4VO3 and (NH4)6Mo7O 24 Preferably, one or more selected from the group consisting of 4H2O.

[0107] When the mixture contains two or more promoter precursors, i.e., when it contains both a vanadium precursor and a molybdenum precursor, the molar ratio of the sum of vanadium and molybdenum to vanadium can be 1:0.45 to 1:0.95 or 1:0.5 to 1:0.9, and preferably 1:0.5 to 1:0.9. When the above conditions are met, the CNT structure can be stably maintained and CNTs with the desired pore volume can be produced.

[0108] The mixture may contain the main catalyst precursor and the co-catalyst precursor such that the molar ratio of the main catalyst to the co-catalyst is 1:0.01 to 1:0.5, 1:0.1 to 1:0.4, or 1:0.1 to 1:0.25, and preferably 1:0.1 to 1:0.25. Satisfying the above molar ratio improves the dispersibility of the main catalyst, enabling the production of CNTs with the desired pore volume.

[0109] The mixture may further include an organic acid which serves to inhibit precipitation of the main catalyst precursor and the co-catalyst precursor.

[0110] The organic acid may be one or more selected from the group consisting of citric acid, tartaric acid, fumaric acid, malic acid, acetic acid, butyric acid, palmitic acid and oxalic acid, with citric acid being preferred.

[0111] The mixture may contain the organic acid and the co-catalyst precursor in a molar ratio of 1:1 to 1:20, 1:2 to 1:10, or 1:3 to 1:6, preferably 1:3 to 1:6. When the above range is satisfied, it is possible to produce a transparent catalyst metal solution during catalyst production, and it is advantageous in that it is possible to produce a catalyst in which fine particles are suppressed during impregnation.

[0112] After step (1), a step of aging may be further included.

[0113] The aging may be carried out for 1 to 60 minutes or 10 to 50 minutes. Preferably, it is carried out for 10 to 50 minutes. When the above conditions are satisfied, the main catalyst precursor and the co-catalyst precursor can be sufficiently supported on the γ-Al2O3. In addition, air bubbles present in the support are removed to the maximum extent possible, and the main catalyst precursor and the co-catalyst precursor can be sufficiently supported even in the fine pores inside the support.

[0114] ·Process (2) The active support is then dried by multi-stage drying, including vacuum drying.

[0115] Multi-stage drying may mean that a drying process including vacuum drying is performed two or more times. Specifically, multi-stage drying may include atmospheric drying and vacuum drying, or may include vacuum drying two or more times.

[0116] The vacuum drying may be carried out at 80° C. to 300° C. or 120° C. to 250° C., preferably at 120° C. to 250° C. If the above conditions are met, the main catalyst precursor, i.e., the coordinate bond of the main catalyst, can be easily decomposed to form the main catalyst oxide, and energy consumption can be minimized.

[0117] The vacuum drying may be performed at 1 mbar to 200 mbar or 30 mbar to 150 mbar, preferably 30 mbar to 150 mbar. When the above conditions are met, the main catalyst precursor, i.e., the main catalyst coordinated compound, is rapidly decomposed and discharged, making it easier to form the main catalyst oxide under vacuum conditions and minimizing energy consumption.

[0118] The vacuum drying can be performed for 10 minutes to 3 hours or 10 minutes to 2 hours, preferably 10 minutes to 2 hours. If the above conditions are met, the main catalyst precursor can be easily decomposed and converted into the main catalyst oxide, and energy consumption can be minimized.

[0119] On the other hand, when the multi-stage drying includes atmospheric drying and vacuum drying, atmospheric drying can be performed before the above-mentioned vacuum drying, and the atmospheric drying can remove solvent that may be present in the active support.

[0120] Drying at normal pressure may be carried out at 80°C to 160°C or 100°C to 140°C, and is preferably carried out at 100°C to 140°C. If the above conditions are met, the solvent present in the active support can be sufficiently removed, and energy consumption can be minimized.

[0121] Drying at atmospheric pressure may be performed at 900 mbar to 1,100 mbar, preferably 950 mbar to 1,050 mbar. If the above conditions are met, the solvent present in the active support can be sufficiently removed and energy consumption can be minimized.

[0122] Drying under atmospheric pressure may be carried out for 1 to 12 hours, preferably 3 to 9 hours. If the above conditions are met, the solvent present in the active support can be sufficiently removed and energy consumption can be minimized.

[0123] On the other hand, when the multi-stage drying includes two or more vacuum dryings, the multi-stage drying may include two or more vacuum dryings performed at different temperatures, more specifically, a primary vacuum drying performed at a first temperature and a secondary vacuum drying performed at a second temperature higher than the first temperature.

[0124] The primary vacuum drying can remove any solvent that may be present in the active support.

[0125] The first temperature may be 80° C. to 160° C., and preferably 100° C. to 140° C. If the above conditions are met, the solvent present in the active support can be sufficiently removed, and energy consumption can be minimized.

[0126] The primary vacuum drying can be carried out for 1 to 12 hours, preferably 3 to 9 hours. If the above conditions are met, the solvent present in the active support can be sufficiently removed and energy consumption can be minimized.

[0127] The primary vacuum drying may be performed at 1 mbar to 200 mbar, 1 mbar to 150 mbar, or 80 mbar to 150 mbar, and is preferably performed at 80 mbar to 150 mbar. If the above conditions are met, the solvent present in the active support can be sufficiently removed, and energy consumption can be minimized.

[0128] The secondary vacuum drying is as described above in the description of vacuum drying.

[0129] The second temperature may be 175 to 300° C., and preferably 180 to 280° C. If the above conditions are met, the main catalyst precursor, i.e., the coordinate bond of the main catalyst, can be easily decomposed to form the main catalyst oxide, and energy consumption can be minimized.

[0130] The secondary vacuum drying may be performed at 1 mbar to 200 mbar, 1 mbar to 150 mbar, or 1 mbar to 70 mbar, and more preferably at 1 mbar to 70 mbar. If the above conditions are met, the main catalyst precursor, i.e., the main catalyst coordinated compound, is rapidly decomposed and discharged, making it easier to form the main catalyst oxide under vacuum conditions and minimizing energy consumption.

[0131] The secondary vacuum drying may be performed for 10 minutes to 3 hours or 10 minutes to 2 hours, preferably 10 minutes to 2 hours. If the above conditions are met, the main catalyst precursor can be easily decomposed and converted into the main catalyst oxide, and energy consumption can be minimized.

[0132] ·Process (3) The dried active support is then subjected to a heat treatment to produce a supported catalyst.

[0133] By carrying out the heat treatment, a supported catalyst is produced in which the main catalyst and the promoter are present in a coated state on the surface and in the pores of γ-Al2O3.

[0134] The heat treatment may be carried out at 600 to 800°C or 620 to 750°C, preferably at 620 to 750°C. If the above conditions are met, a supported catalyst can be produced in which the main catalyst and the co-catalyst are uniformly coated on the surface and pores of the γ-Al2O3, and energy consumption can be minimized.

[0135] The heat treatment may be carried out for 1 to 12 hours or 2 to 8 hours, preferably 2 to 8 hours. When the above-mentioned time is satisfied, a supported catalyst can be produced in which the catalyst precursor is uniformly coated on the surface and in the pores of γ-AlO.

[0136] ·Process (4) CNTs are then produced in the presence of a supported catalyst.

[0137] Specifically, CNTs can be produced by contacting a supported catalyst with a carbon-based compound, and specifically, by chemical vapor synthesis.

[0138] To explain the steps for producing CNTs in detail, first, a supported catalyst is loaded into a horizontal fixed-bed reactor or a fluidized-bed reactor. Next, the gaseous carbon-based compound or a mixture of the gaseous carbon-based compound, a reducing gas (e.g., hydrogen), and a carrier gas (e.g., nitrogen) is injected at a temperature above the thermal decomposition temperature of the gaseous carbon-based compound or below the melting point of the catalyst supported on the supported catalyst. CNTs can be grown by chemical vapor synthesis through the decomposition of the gaseous carbon-based compound.

[0139] The CNTs produced by the above-mentioned chemical vapor synthesis method have a crystal growth direction that is nearly parallel to the tube axis, and the graphite structure has high crystallinity along the tube length. As a result, CNTs with small unit diameters and high conductivity and strength can be produced.

[0140] The chemical vapor synthesis method may be carried out at 600° C. to 800° C. or 650° C. to 750° C., and is preferably carried out at 650° C. to 750° C. If the above temperature is satisfied, CNTs can be produced while minimizing the generation of amorphous carbon.

[0141] The heat source for the reaction may be induction heating, radiant heat, laser, IR, microwave, plasma, surface plasmon heating, or the like.

[0142] Any carbonaceous compound can be used without particular limitations as long as it can supply carbon and can exist in a gaseous state at temperatures of 300° C. or higher.

[0143] The carbon-based compound may be a carbon-based compound having 6 or less carbon atoms, and may be one or more compounds selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene, and toluene.

[0144] After growing CNTs by the above-mentioned reaction, a cooling step may be optionally performed to align the CNTs more regularly. Specifically, the cooling step may be performed by natural cooling by removing the heat source or by using a cooler.

[0145] The above manufacturing methods X and Y are merely examples, and the manufacturing methods for CNTs that can be contained in the specific CNT aggregate are not limited to the above.

[0146] [Carbon nanotube dispersion liquid] The carbon nanotube dispersion liquid (specific CNT dispersion liquid) according to the present disclosure contains a specific CNT aggregate and a dispersion medium. The specific CNT dispersion liquid has good dispersibility of the specific CNT aggregate according to the present disclosure in the dispersion medium, and is also excellent in electrical conductivity. The specific CNT dispersion liquid is preferably used for forming electrodes, forming transparent conductive films, resin additives, conductive inks, coating agents, antistatic agents, paints, and the like.

[0147] <Specific CNT aggregate> The specific CNT aggregate contained in the specific CNT dispersion liquid is the same as the specific CNT aggregate according to the present disclosure described above, and therefore a description thereof will be omitted here.

[0148] <Dispersion medium> The dispersion medium preferably contains water, and more preferably contains water as the main component. "Containing water as a main component" means that the proportion of water in the dispersion medium is more than 50% by mass. The proportion of water in the dispersion medium is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more, and may be, for example, 100% by mass.

[0149] The water is not particularly limited, but is preferably distilled water, ion-exchanged water, pure water, or the like, which contains fewer impurities.

[0150] The dispersion medium may be a mixture of water and a hydrophilic solvent. Examples of hydrophilic solvents include carbonate compounds such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and butylene carbonate; ether compounds such as tetrahydrofuran; ketone compounds such as acetone; lower alcohol compounds such as methanol and ethanol; and solvents such as acetonitrile. When the dispersion medium contains a hydrophilic solvent, the proportion of the hydrophilic solvent in the dispersion medium is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0151] The specific CNT dispersion may further contain other components that can be used in a dispersion, in addition to the specific CNT aggregate and the dispersion medium. Examples of other components include dispersants, antifoaming agents, antistatic agents, conductive assistants other than the conductive assistant according to the present disclosure, etc. Furthermore, the composition may further contain trace amounts of impurity components, so-called inevitable impurities, etc.

[0152] <Dispersant> The carbon nanotube dispersion liquid may contain a dispersant for the purpose of further improving the dispersibility and dispersion stability of the specific CNT aggregates. The dispersant is not particularly limited and may be, for example, various surfactants. The dispersant may also be a polymer compound such as a resin. The dispersant is preferably a surfactant. The surfactant may be an ionic surfactant or a nonionic surfactant, and is not particularly limited. In the specific CNT dispersion, the surfactant may be used alone or in combination of two or more.

[0153] Examples of ionic surfactants include anionic surfactants and cationic surfactants. and amphoteric surfactants. Examples of anionic surfactants include aromatic sulfonic acid surfactants such as alkylbenzenesulfonates (e.g., dodecylbenzenesulfonic acid) and dodecylphenyl ether sulfonates; ether sulfate surfactants; phosphate surfactants; and carboxylic acid surfactants. Examples of cationic surfactants include alkylamine salts and quaternary ammonium salts. Examples of amphoteric surfactants include alkylbetaine surfactants and amine oxide surfactants. As the ionic surfactant, an ionic surfactant having an aromatic ring (so-called aromatic ionic surfactant) is preferred, and aromatic sulfonic acid surfactants such as alkylbenzene sulfonate and dodecyl phenyl ether sulfonate are more preferred. Aromatic ionic surfactants tend to be excellent in dispersibility, dispersion stabilization, and concentration of multi-walled carbon nanotubes.

[0154] Examples of nonionic surfactants include sugar ester surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters; fatty acid ester surfactants such as polyoxyethylene resin acid esters and polyoxyethylene fatty acid diethyl esters; ether surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers and polyoxyethylene polypropylene glycols; and aromatic nonionic surfactants such as polyoxyalkylene octyl phenyl ether, polyoxyalkylene nonyl phenyl ether, polyoxyalkyl dibutyl phenyl ether, polyoxyalkyl styryl phenyl ether, polyoxyalkyl benzyl phenyl ether, polyoxyalkyl bisphenyl ether, polyoxyalkyl cumyl phenyl ether and polyoxyalkylene phenyl ether. As the nonionic surfactant, an ionic surfactant having an aromatic ring (so-called aromatic nonionic surfactant) is preferred, polyoxyalkylene phenyl ether is more preferred, and polyoxyethylene phenyl ether is even more preferred. Aromatic nonionic surfactants tend to be excellent in dispersibility, dispersion stabilization, and concentration of multi-walled carbon nanotubes.

[0155] Other dispersants that are excellent in CNT dispersibility, dispersion stability, and concentration enhancement include β-naphthalenesulfonic acid formalin condensate sodium salts, such as Demol N, Demol RN, and Demol T (manufactured by Kao Corporation), polyoxyethylene stearyl ether Brij S 100 (manufactured by Sigma-Aldrich), polyvinylpyrrolidone K30 (manufactured by, for example, Fujifilm Wako Pure Chemical Industries, Ltd.), carboxymethylcellulose (CMC) (manufactured by, for example, Daicel Miraize Co., Ltd.), sodium deoxycholate (manufactured by, for example, Fujifilm Wako Pure Chemical Industries, Ltd.), and SOLSPERSE TM W100, SOLSPERSE TM W150 (manufactured by Lubrizol Japan, Inc.) is particularly preferred from the viewpoint of excellent dispersibility, dispersion stability and high concentration of multi-walled carbon nanotubes.

[0156] When the specific CNT dispersion liquid contains a dispersant, the amount of the dispersant used is not particularly limited and can be set appropriately depending on the type of dispersant, the amount of multi-walled carbon nanotubes, the amount of dispersion medium, and the like.

[0157] [Method for producing specific CNT dispersion liquid] The method for producing the specific CNT dispersion liquid is not particularly limited. The specific CNT dispersion can be produced by dispersing the specific CNT aggregate in a dispersion medium. That is, the specific CNT dispersion can be produced by a method including a step of dispersing the specific CNT aggregate in a dispersion medium (also referred to as a "dispersion step"). The dispersion medium that can be used in the dispersion step is as described above.

[0158] The dispersion method is not particularly limited. Examples of the dispersion method include methods using a dispersion device such as a stirrer, homogenizer, colloid mill, flow jet mixer, dissolver, paint conditioner, Manton emulsifier, jet mill, and ultrasonic device. Examples of the dispersion method include known pulverization means, such as ball milling (e.g., ball mill, vibration ball mill, planetary ball mill, bead mill, etc.), sand milling, colloid milling, jet milling, roller milling, a vertical or horizontal agitator mill, an attritor, a colloid mill, a three-roll mill, a pearl mill, a super mill, an impeller, a disperser, a KD mill, a dynatron, a pressure kneader, and the like. As a dispersion method, a method using a jet mill is preferred, and a method using a wet jet mill is more preferred. A wet jet mill is a dispersion device that pumps a mixture in a solvent as a high-speed flow through a nozzle arranged in a sealed pressure-resistant container. In a wet jet mill, multi-walled carbon nanotubes are dispersed in the pressure-resistant container by collisions between countercurrent flows, collisions with the container wall, turbulence caused by the high-speed flow, shear flow, etc. As a wet jet mill, an ultra-high-pressure homogenizer (model numbers: NAGS20, NAGS100, JAGS200, NAGS1000, etc.) manufactured by Joko Co., Ltd. can be suitably used. However, the wet jet mill is not limited to this. When the ultra-high pressure homogenizer is used as the dispersing device, the processing pressure for dispersion is preferably 10 MPa to 250 MPa.

[0159] The method for producing the specific CNT dispersion may include a step of drying the specific CNT aggregate (also referred to as a "drying step") before the dispersion step.

[0160] If water adheres to the CNTs, the CNTs tend to adhere to each other due to the surface tension of the water, which may result in a decrease in dispersibility. Therefore, by performing a drying process on the conductive additive before the dispersion process, the water adhered to the CNTs is removed, preventing the multi-walled carbon nanotubes from adhering to each other due to water adhesion, and further improving the dispersibility of the CNTs in the dispersion medium. The drying method is not particularly limited. Examples of drying methods include heat drying, vacuum drying, and heat vacuum drying. The drying method is preferably heated vacuum drying. The drying temperature is not particularly limited, and is preferably 40°C to 100°C, for example. The drying time is not particularly limited and can be set appropriately depending on the drying temperature, the degree of moisture adhering to the multi-walled carbon nanotubes in the present disclosure, and the like.

[0161] An example of the production of the specific CNT dispersion liquid will be shown below, but the production of the specific CNT dispersion liquid is not limited to the following.

[0162] <Production Example 1: Example of production of dispersion liquid> 0.040 g of the specific CNT aggregate according to the present disclosure is weighed and placed in a three-neck flask. After the specific CNT aggregate is placed in the flask, a large excess of ion-exchanged water (e.g., 20 mL) is poured into the flask and stirred at room temperature (25°C, the same applies below). At this time, a known dispersant (e.g., carboxymethyl cellulose) may be added as appropriate. Next, a conductive additive is dispersed in the dispersion medium using a known dispersion device (e.g., an ultrasonic irradiation device or a wet jet mill). The resulting dispersion is further stirred with a stirrer at room temperature for a long period of time (e.g., 1 hour to 48 hours). In this way, a specific CNT dispersion is obtained.

[0163] [Conductive materials] The conductive material according to the present disclosure includes a specific CNT aggregate. As described above, the specific CNT aggregate contained in the conductive material according to the present disclosure has excellent conductivity when made into a dispersion, and is therefore suitable as a conductive auxiliary agent. The conductive material according to the present disclosure contains the specific CT aggregate according to the present disclosure, and therefore has excellent conductive efficiency and can effectively impart high conductivity to the object of use.

[0164] The conductive material according to the present disclosure may contain a known conductive additive such as graphite, Ketjen black, etc. Furthermore, the conductive material according to the present disclosure may contain CNTs other than the specific CNT aggregate.

[0165] The conductive material according to the present disclosure can be used as one of electrode materials. An example of an electrode formed using the electrode material is an electrode included in a secondary battery. Hereinafter, an embodiment of the electrode and the secondary battery including the electrode will be described.

[0166] [Electrodes and secondary batteries] The electrode according to the present disclosure includes an electrode active material and a conductive material according to the present disclosure. The secondary battery according to the present disclosure includes the electrode according to the present disclosure. The electrode according to the present disclosure contains the conductive material according to the present disclosure, and therefore has excellent conductive path formation properties within the electrode, and therefore the secondary battery according to the present disclosure has excellent cycle characteristics. An embodiment of an electrode and a secondary battery including the electrode will be described below.

[0167] <Electrode> The electrode can include a specific CNT aggregate. In the electrode, the specific CNT aggregates can function as a conductive additive. The CNT aggregate contained in the electrode described below is synonymous with the specific CNT aggregate, and the preferred embodiments are also the same, so a description of the CNT aggregate will be omitted below.

[0168] The electrode may be at least one of a positive electrode and a negative electrode. The electrode may include an electrode active material layer, or may include a current collector and an electrode active material layer disposed on the current collector.

[0169] The current collector is not particularly limited as long as it does not induce chemical changes in the battery and has conductivity. The current collector may be, for example, copper, stainless steel, aluminum, nickel, titanium, baked carbon, or aluminum or stainless steel whose surface has been treated with carbon, nickel, titanium, silver, etc. Specifically, a transition metal such as copper or nickel that has good carbon adsorption properties may be used as the current collector.

[0170] The electrode active material layer can include an electrode active material. The electrode active material is preferably electrode active material particles. When the electrode is a positive electrode, the electrode active material is not particularly limited, and the electrode active material layer can contain a positive electrode active material that is commonly used as an electrode material for a positive electrode. Specifically, the positive electrode active material may be a layered compound such as lithium cobalt oxide (LiCoO2) or lithium nickel oxide (LiNiO2), or a compound substituted with one or more transition metals; a lithium iron oxide such as LiFe3O4; or a compound having the chemical formula Li 1+c1 Mn 2-c1Lithium manganese oxides such as O4 (0 ≦ c1 ≦ 0.33), LiMnO3, LiMn2O3, LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, V2O5, Cu2V2O7; chemical formula LiNi 1-c2 M c2 O2 (where M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01 ≦ c2 ≦ 0.66).) Nickel-site type lithium nickel oxide represented by; chemical formula LiMn 2-c3 M c3 O2 (where M is at least one selected from the group consisting of Co, Ni, Fe, Cr, Zn, and Ta, and satisfies 0.01 ≦ c3 ≦ 0.1), or lithium manganese composite oxide represented by Li2Mn3MO8 (where M is at least one selected from the group consisting of Fe, Co, Ni, Cu, and Zn).); examples include LiMn2O4 in which part of the Li in the chemical formula is substituted with an alkaline earth metal ion.

[0171] When the electrode is the negative electrode, the electrode active material is not particularly limited, and the electrode active material layer can contain a negative electrode active material usually used for negative electrode materials. Specifically, the negative electrode active material can contain graphite-based active material particles or silicon-based active material particles. As the graphite-based active material particles, at least one selected from the group consisting of artificial graphite, natural graphite, graphitized carbon fiber, and graphitized mesocarbon microbeads may be used. By using artificial graphite as the graphite-based active material particles, the rate characteristics can be improved. As the silicon-based active material particles, at least one selected from the group consisting of Si, SiOx (0 < x < 2), Si-C composite, and Si-Y alloy (where Y is an element selected from the group consisting of an alkali metal, an alkaline earth metal, a transition metal, a Group 13 element, a Group 14 element, a rare earth element, and combinations thereof) may be used. By using the silicon-based active material particles, the battery can be made to have a higher capacity.

[0172] The electrode active material layer can further contain a binder. The binder is not particularly limited, and the electrode active material layer can contain a binder that is commonly used in electrode materials. Examples of binders include at least one polymer selected from the group consisting of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene propylene diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, and polyacrylic acid, as well as polymers in which the hydrogen atoms of these polymers have been substituted with Li, Na, Ca, or the like.

[0173] <Secondary battery> The secondary battery may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte. At least one of the positive electrode and the negative electrode is an electrode formed using a conductive material containing the specific CNT aggregate as an electrode material.

[0174] The separator separates the negative electrode from the positive electrode and provides a path for lithium ions to move, and is not particularly limited as long as it is a separator that is typically used as a separator in a secondary battery. The separator preferably has low resistance to ion movement of the electrolyte and is excellent in the ability to retain moisture in the electrolyte solution. A specific example of the separator is a porous polymer film. The porous polymer film may be, for example, a porous polymer film made from a polyolefin polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, or an ethylene / methacrylate copolymer, or a laminate structure in which two or more layers of these films are laminated. The separator may also be a typical porous nonwoven fabric, such as a nonwoven fabric made of high-melting-point glass fiber, polyethylene terephthalate fiber, etc. The separator may also be coated with a ceramic component or a polymeric substance to ensure heat resistance or mechanical strength. The separator may optionally be of a single layer or multi-layer structure.

[0175] The electrolyte is not particularly limited, and examples thereof include electrolytes such as organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel-type polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in producing lithium secondary batteries.

[0176] Specifically, the electrolyte can include a non-aqueous organic solvent and a metal salt. Examples of non-aqueous organic solvents include aprotic organic solvents such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl propionate, and ethyl propionate.

[0177] Among carbonate organic solvents, cyclic carbonates such as ethylene carbonate and propylene carbonate are preferred as non-aqueous organic solvents because they have high viscosity and high dielectric constants and dissociate lithium salts well. It is more preferred to use a non-aqueous organic solvent obtained by mixing such cyclic carbonates with linear carbonates having low viscosity and low dielectric constants, such as dimethyl carbonate and diethyl carbonate, in an appropriate ratio, in order to obtain an electrolyte having high electrical conductivity.

[0178] The metal salt may be a lithium salt. Lithium salts are substances that are easily dissolved in non-aqueous electrolytes. The anion portion of the lithium salt may be, for example, F - , Cl - , I - , NO3 - , N(CN)2 - , BF4 - , ClO4 - , PF6 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , CF3SO3 - , CF3CF2SO3 - , (CF3SO2)2N - , (FSO2)2N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , (SF5)3C - , (CF3SO2)3C - , CF3(CF2)7SO3 - , CF3CO2 - , CH3CO2 - , SCN - , and (CF3CF2SO2)2N - Examples include:

[0179] In addition to the non-aqueous organic solvent and metal salt, the electrolyte may further contain one or more additives such as haloalkylene carbonate compounds such as difluoroethylene carbonate, pyridine, triethyl phosphite, triethanolamine, cyclic ethers, ethylenediamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivatives, sulfur, quinoneimine dyes, N-substituted oxazolidinones, N,N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrrole, 2-methoxyethanol, and aluminum trichloride, for the purposes of improving the battery's life characteristics, suppressing a decrease in battery capacity, and improving the battery's discharge capacity.

[0180] The above-described secondary battery can be used to form a battery module including the secondary battery as a unit cell, and a battery pack including the battery module. The battery module and the battery pack can be used as a power source for a medium to large device selected from the group consisting of, for example, an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system.

[0181] [Planar aggregate] The planar aggregate according to the present disclosure includes a specific CNT aggregate, and the specific CNT aggregate includes CNTs having a maximum length of 1000 μm to 30000 μm. The proportion of CNTs having a maximum length of 1000 μm to 30000 μm contained in the planar aggregate according to the present disclosure is usually 1 mass % or more. The planar aggregate according to the present disclosure may include other components such as carbon nanotube aggregates having a maximum length of less than 1000 μm, i.e., CNT aggregates that do not include carbon nanotubes having a maximum length of 1000 μm to 30000 μm.

[0182] [Method for producing a planar assembly] The method for producing the planar assembly according to the present disclosure is not particularly limited. The planar aggregate according to the present disclosure can be produced, for example, as a nonwoven fabric-like planar aggregate by dispersing CNT aggregates having a maximum length of 1000 μm to 30000 μm, or CNT aggregates having a maximum length of 1000 μm to 30000 μm and other components such as carbon nanotube aggregates having a maximum length of less than 1000 μm, in water or other fluid and filtering the resultant once or twice or more times.

[0183] An example of the planar assembly according to the present disclosure is a film. Planar assemblies according to the present disclosure are useful, for example, in filters, electromagnetic shields, and extreme ultraviolet (EUV) pellicles. [Example]

[0184] The specific CNT aggregate, dispersion containing the specific CNT aggregate, and the like according to the present disclosure will be described in more detail below with reference to examples. The aggregate and dispersion according to the present disclosure are not limited to the following examples as long as they do not deviate from the gist of the disclosure. Unless otherwise specified, "%" means "% by mass".

[0185] Example 1 1. Production of sheet-shaped CNT aggregate 1 Sheet-like CNT aggregate 1 was prepared by the floating catalyst method (CVD method) which directly interacts with the self-assembly of CNT bundles in the gas phase. First, ferrocene as a metal catalyst precursor containing Fe atoms and thiophene as a promoter were introduced into a continuous flow of carrier gas in a once-through reactor whose temperature was controlled between 400 and 700°C. A mixture of nitrogen and argon was used as the carrier gas. The flow rate of the carrier gas was 30,000 sccm (standard cubic centimeters per minute). By maintaining the temperature in the once-through reactor within the above range, the metal catalyst precursor was produced as a particulate metal catalyst. The region where the metal catalyst was produced is referred to as the first temperature zone.

[0186] Next, methane, a carbon source, was released into the carrier gas stream. The metal catalyst and carbon source were fed into a second temperature zone downstream of the first temperature zone, which was controlled at 1400°C. The second temperature zone was maintained at a temperature sufficient to produce carbon nanotube aggregates.

[0187] In the second temperature zone, an electric field was generated within the temperature-controlled flow reactor, which generated CNT aggregates. The aggregates of CNTs were continuously discharged through the outlet of a flow-type reactor whose temperature was controlled at 100°C to 500°C, and a sheet-like CNT aggregate was collected by continuous discharge. The obtained sheet-like CNT aggregate contains MWCNTs. The obtained sheet-like CNT aggregate was washed with pure water for 10 seconds to obtain a sheet-like CNT aggregate 1, which is a specific CNT aggregate.

[0188] 2. Preparation of CNT Dispersion 1 The following materials were mixed and pre-dispersed by processing for 1 hour using an Ace Homogenizer manufactured by Nippon Seiki Co., Ltd. to obtain pre-dispersion 1. Note that the sheet-like CNT aggregate 1 was cut into small pieces measuring 1 cm x 1 cm with scissors before mixing to prevent the sheet-like CNT aggregate 1 from becoming tangled in the blades of the homogenizer.

[0189] (Dispersion liquid composition) 1.1g of the sheet-like CNT aggregate 1 obtained above ·CARBOXYMETHYL CELLULOSE SODIUM SALT HIGH VISCOSITY (manufactured by MP Biomedicals) 1.65g ·Pure water 547.25g

[0190] The pre-dispersion liquid 1 was subjected to main dispersion using an ultra-high pressure homogenizer (model number: NAGS100) manufactured by Joko Corporation as a wet jet mill under the following conditions to obtain CNT dispersion liquid 1, which is a specific CNT dispersion liquid. (dispersion condition) Nozzle diameter: 0.22 mm Pressure: 85 MPa Number of times: 8 Method: Circulation method

[0191] 3. Evaluation 3-1. Pore volume and BET specific surface area The pore volume and BET specific surface area were measured using a gas adsorption measurement device (product name "BELSORP-miniII", manufactured by Microtrack-Bell). The sheet-shaped CNT aggregate 1 obtained in Example 1 was used as a measurement sample. The pore volume was measured after the sheet-like CNT aggregate 1 was subjected to vacuum degassing treatment at 300°C for 3 hours using a pretreatment device (product name "BELPREP-vacII", manufactured by Microtrac-Bel). For the sheet-shaped CNT aggregate 1 after the vacuum degassing treatment, the adsorption / desorption isotherm with nitrogen was measured using a constant volume method. The measurement temperature was 77 K, the adsorbate was nitrogen, the saturated vapor pressure was measured, and the adsorbate cross section was 0.162 nm 2 The waiting time after the adsorption equilibrium state was reached was set to 500 seconds. The pore volume was calculated from the obtained adsorption / desorption isotherms using the BJH method. As a result, the pore volume of the sheet-like CNT aggregate 1 was 2.06 cm 3 / g. The BET method (BET-Plot) was used for analysis to calculate the BET specific surface area from the obtained adsorption / desorption isotherms. As a result, the BET specific surface area of ​​the sheet-like CNT aggregate 1 was 178 m 2 / g.

[0192] 3-2.Volume resistivity The sheet-like CNT aggregate 1 of Example 1 was pulverized using a freeze-pulverization method. Using a Loresta device (product name: powder resistivity measurement system MCP-PD51, low resistivity meter Loresta-GP, low resistance probe for powder MCP-PD511 (constant current application type 4-probe method), all manufactured by Nitto Seiko Analytech Co., Ltd.), the pulverized sheet-like CNT aggregate 1 was introduced into a powder resistivity measurement probe unit, and pressed at 1 kN and 20 kN using the attached hydraulic pump until the target load was reached, at which point the volume resistivity (Ω cm) was measured. As a result, the volume resistivity was 1.7 × 10 at 1 kN. -2 Ω·cm, and 5.0×10 at 20 kN -3 The ratio of the volume resistivity at 20 kN to the volume resistivity at 1 kN (referred to as "resistivity ratio" in Table 1) was 0.29.

[0193] 3-3. Checking the bundle structure The obtained sheet-like CNT aggregate 1 of Example 1 was observed with an SEM (device name: S-4800, manufactured by Hitachi High-Technologies Corporation), and it was confirmed that it contained a bundle structure. Measurements were taken at 20 points, and the average value was calculated, and the width of the bundle structure was found to be 70 nm.

[0194] 3-4. Conductivity of dispersion liquid CNT dispersion liquid 1 was dropped onto a glass substrate (10 cm × 10 cm) and formed into a film using a stainless steel applicator with a gap size of 150 μm, and then heated on a hot plate at 110°C for 10 minutes to dry. The surface resistivity of the film was measured using Loresta GXII manufactured by Nitto Seiko Analytech Co., Ltd. Measurements were taken at five points on the film, and the average of the five values ​​was taken as the surface resistivity. As a result, the surface resistivity was 164.42 Ω / □.

[0195] The evaluation results are shown in Table 1.

[0196] Example 2 1. Preparation of Fibrous CNT Aggregates 2 Like the sheet-like CNT aggregate 1, the fibrous CNT aggregate 2 was also produced by the floating catalyst method (CVD method) which directly interacts with the self-assembly of CNT bundles in the gas phase. First, ferrocene as a metal catalyst precursor containing Fe atoms and thiophene as a promoter were introduced into a continuous flow of carrier gas in a once-through reactor whose temperature was controlled between 400 and 700°C. A mixture of nitrogen and argon was used as the carrier gas. The flow rate of the carrier gas was 30,000 sccm. By maintaining the temperature in the once-through reactor within the above range, the metal catalyst precursor was produced as a particulate metal catalyst. The region where the metal catalyst was produced is referred to as the first temperature zone.

[0197] Next, methane, a carbon source, was released into the carrier gas stream. The metal catalyst and carbon source were fed into a second temperature zone downstream of the first temperature zone, which was controlled at 1400°C. The second temperature zone was maintained at a temperature sufficient to produce carbon nanotube aggregates.

[0198] In the second temperature zone, an electric field was generated within the temperature-controlled flow reactor, which produced fibrous CNT aggregates. The carbon nanotube aggregates were continuously discharged through the outlet of a flow-type reactor whose temperature was controlled at 100°C to 500°C, and fibrous CNT aggregates were collected by continuous discharge. The obtained fibrous CNT aggregate contains MWCNTs. The obtained fibrous CNT aggregate was washed with pure water for 10 seconds, and a fibrous CNT aggregate 2 was obtained.

[0199] 2. Preparation of CNT Dispersion 2 Using the obtained fibrous CNT aggregate 2, a CNT dispersion liquid 2 was obtained in the same manner as in Example 1.

[0200] 3. Evaluation The fibrous CNT aggregate 2 and CNT dispersion 2 of Example 2 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0201] Example 3 1. Production of sheet-shaped CNT aggregate 3 A sheet-like CNT aggregate 3 was produced in accordance with Example 1, except that the obtained sheet-like CNT aggregate was not washed with pure water.

[0202] 2. Preparation of CNT Dispersion 3 Using the obtained sheet-shaped CNT aggregate 3, a CNT dispersion 3 was obtained in the same manner as in Example 1.

[0203] 3. Evaluation The sheet-shaped CNT aggregate 3 and the CNT dispersion 3 of Example 3 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0204] (Comparative Example 1) 1. Preparation of Powdered CNT Aggregates 4 As the powdered CNT aggregate 4, "multi-walled carbon nanotubes" (catalog number: 901019, 50-90 nm diameter, >95% carbon basis, manufactured by Sigma-Aldrich) were prepared.

[0205] 2. Preparation of CNT Dispersion 4 Using the prepared powdered CNT aggregate 4, a CNT dispersion liquid 4 was obtained in the same manner as in Example 1.

[0206] 3. Evaluation The powdered CNT aggregate 4 and the CNT dispersion liquid 4 of Comparative Example 1 were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0207] (Comparative Example 2) 1. Preparation of Powdered CNT Aggregates 5 As the powdered CNT aggregate 5, "multi-walled carbon nanotubes" (catalog number: "FT7000, manufactured by C-nano Co., Ltd.) were prepared.

[0208] 2. Preparation of CNT Dispersion 4 Using the prepared powdered CNT aggregate 5, a CNT dispersion liquid 5 was obtained in the same manner as in Example 1.

[0209] 3. Evaluation The powdered CNT aggregate 4 and the CNT dispersion liquid 4 of Comparative Example 2 were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0210] [Table 1]

[0211] In Table 1, "-" in the bundle structure column indicates that the bundle structure could not be confirmed.

[0212] As shown in Table 1, it is clear that the CNT dispersion obtained by dispersing the CNT aggregates of the examples has good electrical conductivity. On the other hand, the pore volume is 0.60 cm 3 / g, the CNT aggregate of Comparative Example 1 had a problem with the conductivity of the CNT dispersion obtained by dispersing it. It is clear that the CNT aggregate of Comparative Example 1 is inferior as a conductive material. Furthermore, the CNT aggregate of Comparative Example 2, in which the ratio of the volume resistivity at 20 kN to the volume resistivity at 1 kN was less than 0.18, had a problem with the conductivity of the CNT dispersion obtained by dispersing it. It is clear that the CNT aggregate of Comparative Example 2 is inferior as a conductive material.

Claims

1. An aggregate of carbon nanotubes that satisfies the following conditions (1) and (2): (1) Pore volume is 0.60 cm ３ / g to 5.00 cm ３ / g. (2) The ratio of the volume resistivity under a pressure of 20 kN to the volume resistivity under a pressure of 1 kN is 0.18 or more and 0.30 or less.

2. The carbon nanotube aggregate according to claim 1 , which comprises a bundle structure.

3. BET specific surface area is 100m ２ / g~420m ２ The carbon nanotube aggregate according to claim 1 or 2, wherein the aggregate has a surface area of ​​1 / g.

4. A carbon nanotube dispersion liquid comprising the aggregate of carbon nanotubes according to claim 1 or 2 and a dispersion medium.

5. A conductive material comprising the carbon nanotube aggregate according to claim 1 or 2.

6. An electrode comprising an electrode active material and the conductive material according to claim 5 .

7. A secondary battery comprising the electrode according to claim 6.

8. 3. A planar aggregate comprising the carbon nanotube aggregate according to claim 1 or 2, wherein the carbon nanotube aggregate comprises carbon nanotubes having a maximum length of 1000 μm to 30000 μm.

9. A filter using the planar assembly according to claim 8.

10. An electromagnetic wave shield using the planar assembly according to claim 8.

11. A pellicle for extreme ultraviolet rays, which uses the planar assembly according to claim 8.

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